Primary intermediates for oxidative coloration of hair

ABSTRACT

Primary intermediates for hair coloring compositions for oxidative dyeing of hair are compounds of the formula (1):  
                 
 
     wherein R is hydrogen, hydroxy, nitro, amino, halogen, C 1  to C 5  alkyl or haloalkyl, C 1  to C 5  alkoxy or cyclic alkoxy, C 1  to C 5  hydroxyalkyl and C 1  to C 5  hydroxyalkoxy; Ar is an aromatic group; and y=1 to 3.

FIELD OF THE INVENTION

[0001] This invention relates to a new2-(1-aryloxy-ethyl)-benzene-1,4-diamine compounds and compositionscontaining these new compounds as primary intermediates for oxidativecoloring of hair fibers.

BACKGROUND OF THE INVENTION

[0002] Coloration of hair is a procedure practiced from antiquityemploying a variety of means. In modern times, the method mostextensively to color hair is an oxidative dyeing process utilizing oneor more oxidative hair coloring agents in combination with one or moreoxidizing agents.

[0003] Most commonly a peroxy oxidizing agent is used in combinationwith one or more oxidative hair coloring agents, generally smallmolecules capable of diffusing into hair and comprising one or moreprimary intermediates and one or more couplers. In this procedure, aperoxide material, such as hydrogen peroxide, is employed to activatethe small molecules of primary intermediates so that they react withcouplers to form larger sized compounds in the hair shaft to color thehair in a variety of shades and colors.

[0004] A wide variety of primary intermediates and couplers have beenemployed in such oxidative hair coloring systems and compositions. Amongthe primary intermediates employed there may be mentionedp-phenylenediamine, p-toluenediamine, p-aminophenol,4-amino-3-methylphenol, N,N-bis(2-hydroxyethyl)-p-phenylene diamine,1-(2-hydroxyethyl)-4,5-diaminopyrazole and as couplers there may bementioned resorcinol, 2-methylresorcinol, 3-aminophenol,2,4-diaminophenoxyethanol, and 5-amino-2-methylphenol.

[0005] There are numerous additional requirements for oxidation dyecompounds that are used to dye human hair besides the color or thedesired intensity. Thus, the dye compounds must be unobjectionable inregard to toxicological and dermatological properties and must providethe desired hair color with a good light fastness, fastness to apermanent wave treatment, acid fastness and fastness to rubbing. Thecolor of the hair dyed with the dye compounds in each case must bestable for at least 4 to 6 weeks to light, rubbing and chemical agents.Furthermore, an additional requirement is the production of a broadpalette of different color shades using different developer and couplersubstances. A majority of the desired shades have been produced withdyes based on p-phenylenediamine. However, the use of p-phenylenediamineis being questioned, mainly due to sensitization potential. GB2,239,265A describes that some individuals are becoming sensitized top-phenylenediamine and its derivatives.. The proposed replacements forp-phenylenediamine have not proved entirely satisfactory. There istherefore a need for new primary intermediate compounds to meet one ormore of the desired properties but not possessing the sensitizationpotential possessed by p-phenylenediamine, that is, which has a weakersensitization potential than p-phenylenediamine.

SUMMARY OF THE INVENTION

[0006] It is therefore an object of this invention to provide newprimary intermediate compound useful in place of p-phenylenediamine toprovide a wide range of different color shades with various combinationsof primary intermediates and couplers, but which has a weakersensitization potential than p-phenylenediamine.

[0007] It has been discovered that the new2-(1-aryloxy-ethyl)-benzene-1,4-diamine compounds are suitable primaryintermediates for hair coloring compositions with less sensitizationpotential than p-phenylenediamine and systems for providing goodoxidative coloration of hair and for providing acceptable lightfastness, fastness to shampooing, good selectivity, fastness toperspiration and permanent wave treatment, and suitable for providing awide variety of different color shades with various primary intermediateand coupler compounds.

[0008] The invention provides new2-(1-aryloxy-ethyl)-benzene-1,4-diamine compounds of formula (1):

[0009] wherein R is hydrogen, hydroxy, nitro, amino, halogen, C₁ to C₅alkyl or haloalkyl, C₁ to C₅ alkoxy or cyclic alkoxy, C₁ to C₅hydroxyalkyl and C₁ to C₅ hydroxyalkoxy; Ar is an aromatic group,preferably an aromatic group selected from a furanyl, thienyl,pyridinyl, phenyl, 2,3-dihydro-benzo[1,4]dioxin-5 or-6-yl orbenzo[1,3]dioxol-4 or -5-yl group; and y=1 to 3. The halogen may befluorine, chlorine, bromine or iodine, preferable fluorine or chlorine.

[0010] These novel primary intermediates are used to provide colorationto hair in which there is good dye uptake by the hair and providesshades or colors which are stable over a relatively long period of time.The novel primary intermediates provides for dyeing of hair to impartcolor or shades that possess good wash fastness and do not undergosignificant changes on exposure to light, shampooing or perspiration.

DETAILED DESCRIPTION OF THE INVENTION

[0011] Preferred compounds of formula (1) of this invention are thosewherein R is hydrogen, amino or C₁ to C₃ alkyl, and Ar is phenyl,pyridinyl, furanyl, 2- or 3-thienyl, 2,3-dihydro-benzo[1,4]dioxin-5 or-6-yl or benzo[1,3]dioxol-4 or -5-yl.

[0012] The new 2-(1-aryloxy-ethyl)benzene-1,4-diamine compounds offormula (1) of this invention can be prepared according to the followingreaction sequence, where R₁ and R₂ are as defined hereinbefore.

[0013] In this synthesis procedure reduction of a compound of formula(2) with a reducing agent such as sodium borohydride (NaBH₄) produces acompound of formula (3). Catalytic hydrogenation of the compound offormula (3) provides a compound of formula (4). Bytert-butoxycarbonylation of the compound of formula (4) withdi-tert-butyl dicarbonate ((Boc)₂O) in acetonitrile gives the compoundof formula (5). Subjecting the compound of formula (5) to the Mitsunobureaction with a compound of the formula HO—Ar—(R)_(y) in the presence oftriphenyl phosphine and diethyl azodicarboxylate or diisopropylazodicarboxylate produces a compound of formula (6). Treatment of thecompound of formula (6) with methanolic HCI results in a compound offormula (1) of this invention.

SYNTHESIS EXAMPLES 1 to 11

[0014] Employing the appropriate compound of the formula HO—Ar—(R)y inthis synthesis procedure produces the following compounds:

[0015] 2-(1-phenoxy-ethyl)-benzene-1,4-diamine;

[0016] 2-[1-(4-amino-3-methyl-phenoxy)-ethyl]-benzene-1,4-diamine;

[0017] 2-[1-(pyridin-3-yloxy)-ethyl]-benzene-1,4-diamine;

[0018] 2-[1-thien-2-yloxy)-ethyl]-benzene-1,4-diamine;

[0019] 2-[1-(furan-2-yloxy)-ethyl]-benzene-1,4-diamine;

[0020] 2-[1-(4-amino-phenoxy)-ethyl]-benzene-1,4-diamine;

[0021] 2-{1-(2,3-dihydro-benzo[1 ,4]dioxin-6-yloxy)-ethyl}-benzene-1,4-diamine;

[0022] 2-[1-(5-bromo-furan-2yloxy)-ethyl]-benzene-1 ,4-diamine;

[0023] 2-[1-(4-chloromethyl-phenoxy)-ethyl]-benzene-1 ,4-diamine;

[0024] 2-[1-(4-methoxy-phenoxy)-ethyl]-benzene-1,4-diamine; and

[0025] 2-{1-(benzo[1,3]dioxin-5yloxy)-ethyl}-benzene-1,4-diamine.

[0026] As used herein, the term “hair dyeing composition” (alsosynonymously referred to herein as the hair dye composition, the haircoloring composition, or the hair dye lotion) refers to the compositioncontaining oxidation dyes, including the novel compounds describedherein, prior to admixture with the developer composition. The term“developer composition” (also referred to as the oxidizing agentcomposition or the peroxide composition) refers to compositionscontaining an oxidizing agent prior to admixture with the hair dyeingcomposition. The term “hair dye product” or “hair dye system” (alsoreferred to as the hair dyeing system, hair dyeing product, or haircoloring system) interchangeably refer to the combination of the hairdyeing composition and the developer composition before admixture, andmay further include a conditioner product and instructions, such productor system often being provided packaged as a kit. The term “hair dyeingproduct composition” refers to the composition formed by mixing the hairdyeing composition and the developer composition. “Carrier” (or vehicleor base) refers to the combination of ingredients contained in acomposition excluding the active agents (e.g., the oxidation hair dyesof the hair dyeing composition).

[0027] Hair coloring (i.e., hair dyeing) compositions of this inventioncan contain, in combination with oxidation dye couplers, a novel primaryintermediate of this invention as the sole primary intermediate or canalso contain other primary intermediates. Thus, one or more suitableprimary intermediates may be used in combination with the novel primaryintermediates of this invention.

[0028] Suitable known primary intermediates include, for example,

[0029] p-phenylenediamine derivatives such as: benzene-1,4-diamine(commonly known as p-phenylenediamine), 2-methyl-benzene-1,4-diamine,2-chloro-benzene-1,4-diamine, N-phenyl-benzene-1,4-diamine,N-(2-ethoxyethyl)benzene-1,4-diamine,2-[(4-amino-phenyl)-(2-hydroxy-ethyl)-amino]-ethanol, (commonly known asN,N-bis(2-hydroxyethyl)-p-phenylenediamine)(2,5-diamino-phenyl)-methanol, 1-(2,5-diamino-phenyl)-ethanol,2-(2,5-diamino-phenyl)-ethanol, N-(4-aminophenyl)benzene-1,4-diamine,2,6-dimethyl-benzene-1,4-diamine, 2-isopropyl-benzene-1,4-diamine,1-[(4-aminophenyl)amino]-propan-2-ol, 2-propyl-benzene-1,4-diamine,1,3-bis[(4-aminophenyl)(2-hydroxyethyl)amino]propan-2-ol,N⁴,N⁴,2-trimethylbenzene-1,4-diamine, 2-methoxy-benzene-1,4-diamine,1-(2,5-diaminophenyl)ethane-1,2-diol, 2,3-dimethyl-benzene-1,4-diamine,N-(4-amino-3-hydroxy-phenyl)-acetamide, 2,6-diethylbenzene-1,4-diamine,2,5-dimethylbenzene-1,4-diamine, 2-thien-2-ylbenzene-1,4-diamine,2-thien-3-ylbenzene-1,4-diamine, 2-pyridin-3-ylbenzene-1,4-diamine,1,1′-biphenyl-2,5-diamine, 2-(methoxymethyl )benzene-1,4-diamine,2-(aminomethyl )benzene-1,4-diamine, 2-(2,5-diaminophenoxy)ethanol,N-[2-(2,5-diaminophenoxy)ethyl]-acetamide,N,N-dimethylbenzene-1,4-diamine, N,N-diethylbenzene-1,4-diamine,N,N-dipropylbenzene-1,4-diamine, 2-[(4-aminophenyl)(ethyl)amino]ethanol,2-[(4-amino-3-methyl-phenyl)-(2-hydroxy-ethyl)-amino]-ethanol,N-(2-methoxyethyl)-benzene-1,4-diamine,3-[(4-aminophenyl)amino]propan-1-ol,3-[(4-aminophenyl)-amino]propane-1,2-diol,N-{4-[(4-aminophenyl)amino]butyl}benzene-1,4-diamine, and2-[2-(2-{2-[(2,5-diaminophenyl)-oxy]ethoxy}ethoxy)ethoxy]benzene-1,4-diamine;

[0030] p-aminophenol derivatives such as: 4-amino-phenol (commonly knownas p-aminophenol), 4-methylamino-phenol, 4-amino-3-methyl-phenol,4-amino-2-hydroxymethyl-phenol, 4-amino-2-methyl-phenol,4-amino-2-[(2-hydroxy-ethylamino)-methyl]-phenol,4-amino-2-methoxymethyl-phenol, 5-amino-2-hydroxy-benzoic acid,1-(5-amino-2-hydroxy-phenyl)-ethane-1 ,2-diol,4-amino-2-(2-hydroxy-ethyl)-phenol, 4-amino-3-(hydroxymethyl )phenol,4-amino-3-fluoro-phenol, 4-amino-2-(aminomethyl)-phenol, and4-amino-2-fluoro-phenol;

[0031] o-aminophenol derivatives such as: 2-amino-phenol (commonly knownas o-aminophenol), 2,4-diaminophenol, 2-amino-5-methyl-phenol,2-amino-6-methyl-phenol, N-(4-amino-3-hydroxy-phenyl)-acetamide, and2-amino-4-methyl-phenol; and

[0032] heterocyclic derivatives such as: pyrimidine-2,4,5,6-tetramine(commonly known as 2,4,5,6-tetraaminopyridine),1-methyl-1H-pyrazole-4,5-diamine,2-(4,5-diamino-1H-pyrazol-1-yl)ethanol, N²,N²-dimethyl-pyridine-2,5-diamine,2-[(3-amino-6-methoxypyridin-2-yl)amino]ethanol,6-methoxy-N²-methyl-pyridine-2,3-diamine,2,5,6-triaminopyrimidin-4(1H)-one, pyridine-2,5-diamine,1-isopropyl-1H-pyrazole-4,5-diamine,1-(4-methylbenzyl)-1H-pyrazole-4,5-diamine,1-(benzyl)-1H-pyrazole-4,5-diamine, and1-(4-chlorobenzyl)-1H-pyrazole-4,5-diamine.

[0033] The novel primary intermediates of formula (1) of this inventionmay be used with any suitable coupler(s) in hair coloring compositionsor systems of this invention.

[0034] Suitable known couplers include, for example:

[0035] phenols, resorcinol and naphthol derivatives such as:naphthalene-1,7-diol, benzene-1,3-diol, 4-chlorobenzene-1,3-diol,naphthalen-1-ol, 2-methyl-naphthalen-1-ol, naphthalene-1,5-diol,naphthalene-2,7-diol, benzene-1 ,4-diol, 2-methyl-benzene-1,3-diol,7-amino-4-hydroxy-naphthalene-2-sulfonic acid,2-isopropyl-5-methylphenol, 1,2,3,4-tetrahydro-naphthalene-1,5-diol,2-chloro-benzene-1,3-diol, 4-hydroxy-naphthalene-1-sulfonic acid,benzene-1,2,3-triol, naphthalene-2,3-diol,5-dichloro-2-methylbenzene-1,3-diol, 4,6-dichlorobenzene-1,3-diol, and2,3-dihydroxy-[1,4]naphthoquinone;

[0036] m-phenylenediamines such as: 2,4-diaminophenol,benzene-1,3-diamine, 2-(2,4-diamino-phenoxy)-ethanol,2-[(3-amino-phenyl)-(2-hydroxy-ethyl)-amino]-ethanol,2-mehyl-benzene-1,3-diamine,2-[[2-(2,4-diamino-phenoxy)-ethyl]-(2-hydroxy-ethyl)-amino]-ethanol,4-{3-[(2,4-diaminophenyl)oxy]propoxy}benzene-1,3-diamine,2-(2,4-diamino-phenyl)-ethanol,2-(3-amino-4-methoxy-phenylamino)-ethanol,4-(2-amino-ethoxy)-benzene-1,3-diamine, (2,4-diamino-phenoxy)-aceticacid, 2-[2,4-diamino-5-(2-hydroxy-ethoxy)-phenoxy]-ethanol,4-ethoxy-6-methyl-benzene-1,3-diamine, 2-(2,4-diamino-5-methyl-phenoxy)-ethanol, 4,6-dimethoxy-benzene-1,3-diamine,2-[3-(2-hydroxy-ethylamino)-2-methyl-phenylamino]-ethanol,3-(2,4-diamino-phenoxy)-propan-1-ol, N-[3-(dimethylamino)phenyl]urea,4-methoxy-6-methylbenzene-1,3-diamine,4-fluoro-6-methylbenzene-1,3-diamine,2-({3-[(2-hydroxyethyl)amino]-4,6-dimethoxyphenyl}-amino)ethanol,3-(2,4-diaminophenoxy)-propane-1,2-diol,2-[2-amino-4-(methylamino)-phenoxy]ethanol,2-[(5-amino-2-ethoxy-phenyl)-(2-hydroxy-ethyl)-amino]-ethanol,2-[(3-aminophenyl)amino]ethanol, N-(2-aminoethyl)benzene-1,3-diamine,4-{[(2,4-diamino-phenyl)oxy]methoxy}-benzene-1,3-diamine, and2,4-dimethoxybenzene-1,3-diamine;

[0037] m-aminophenols such as: 3-amino-phenol,2-(3-hydroxy-4-methyl-phenylamino)-acetamide,2-(3-hydroxy-phenylamino)-acetamide, 5-amino-2-methyl-phenol,5-(2-hydroxy-ethylamino)-2-methyl-phenol, 5-amino-2,4-dichloro-phenol,3-amino-2-methyl-phenol, 3-amino-2-chloro-6-methyl-phenol,5-amino-2-(2-hydroxy-ethoxy)-phenol,2-chloro-5-(2,2,2-trifluoro-ethylamino)-phenol,5-amino-4-chloro-2-methyl-phenol, 3-cyclopentylamino-phenol,5-[(2-hydroxyethyl)amino]-4-methoxy-2-methylphenol,5-amino-4-methoxy-2-methylphenol, 3-(dimethylamino)phenol,3-(diethylamino)phenol, 5-amino-4-fluoro-2-methylphenol,5-amino-4-ethoxy-2-methylphenol, 3-amino-2,4-dichloro-phenol,3-[(2-methoxyethyl)amino]phenol, 3-[(2-hydroxyethyl)amino]phenol,5-amino-2-ethyl-phenol, 5-amino-2-methoxyphenol,5-[(3-hydroxypropyl)amino]-2-methylphenol,3-[(3-hydroxy-2-methylphenyl)-amino]propane-1,2-diol, and3-[(2-hydroxyethyl)amino]-2-methylphenol; and

[0038] heterocyclic derivatives such as:3,4-dihydro-2H-1,4-benzoxazin-6-ol,4-methyl-2-phenyl-2,4-dihydro-3H-pyrazol-3-one,6-methoxyquinolin-8-amine, 4-methylpyridine-2,6-diol,2,3-dihydro-1,4-benzodioxin-5-ol, 1,3-benzodioxol-5-ol,2-(1,3-benzodioxol-5-ylamino)ethanol, 3,4-dimethylpyridine-2,6-diol,5-chloropyridine-2,3-diol, 2,6-dimethoxypyridine-3,5-diamine,1,3-benzodioxol-5-amine,2-{[3,5-diamino-6-(2-hydroxy-ethoxy)-pyridin-2-yl]oxy}-ethanol,1H-indol-4-ol, 5-amino-2,6-dimethoxypyridin-3-ol, 1H-indole-5,6-diol,1H-indol-7-ol, 1H-indol-5-ol, 1H-indol-6-ol,6-bromo-1,3-benzodioxol-5-ol, 2-aminopyridin-3-ol, pyridine-2,6-diamine,3-[(3,5-diaminopyridin-2-yl)oxy]propane-1,2-diol,5-[(3,5-diaminopyridin-2-yl)oxy]pentane-1,3-diol, 1H-indole-2,3-dione,indoline-5,6-diol, 3,5-dimethoxypyridine-2,6-diamine,6-methoxypyridine-2,3-diamine, and 3,4-dihydro-2H-1,4-benzoxazin-6-amine.

[0039] Preferred primary intermediates include:

[0040] p-phenylenediamine derivatives such as:2-methyl-benzene-1,4-diamine, benzene-1,4-diamine,1-(2,5-diamino-phenyl)-ethanol, 2-(2,5-diamino-phenyl)-ethanol,N-(2-methoxyethyl)benzene-1,4-diamine,2-[(4-amino-phenyl)-(2-hydroxy-ethyl)-amino]-ethanol, and1-(2,5-diaminophenyl)ethane-1,2-diol;

[0041] p-aminophenol derivatives such as 4-amino-phenol,4-methylamino-phenol, 4-amino-3-methyl-phenol,4-amino-2-methoxymethyl-phenol, and1-(5-amino-2-hydroxy-phenyl)-ethane-1,2-diol;

[0042] o-aminophenol derivatives such as: 2-amino-phenol,2-amino-5-methyl-phenol, 2-amino-6-methyl-phenol,N-(4-amino-3-hydroxy-phenyl)-acetamide, and 2-amino-4-methyl-phenol; and

[0043] heterocyclic derivatives such as: pyrimidine-2,4,5,6-tetramine,1-methyl-1H-pyrazole-4,5-diamine,2-(4,5-diamino-1H-pyrazol-1-yl)ethanol,1-(4-methylbenzyl)-1H-pyrazole-4,5-diamine,1-(benzyl)-1H-pyrazole-4,5-diamine, andN²,N²-dimethyl-pyridine-2,5-diamine.

[0044] Preferred couplers include:

[0045] phenols, resorcinol and naphthol derivatives such as:naphthalene-1,7-diol, benzene-1,3-diol, 4-chlorobenzene-1,3-diol,naphthalen-1-ol, 2-methyl-naphthalen-1-ol, naphthalene-1,5-diol,naphthalene-2,7-diol, benzene-1,4-diol, 2-methyl-benzene-1,3-diol, and2-isopropyl-5-methylphenol;

[0046] m-phenylenediamines such as: benzene-1,3-diamine,2-(2,4-diamino-phenoxy)-ethanol,4-{3-[(2,4-diaminophenyl)oxy]propoxy}benzene-1,3-diamine ,2-(3-amino-4-methoxy-phenylamino)-ethanol,2-[2,4-diamino-5-(2-hydroxy-ethoxy)-phenoxy]-ethanol, and3-(2,4-diamino-phenoxy)-propan-1-ol;

[0047] m-aminophenols such as: 3-amino-phenol, 5-amino-2-methyl-phenol,5-(2-hydroxy-ethylamino)-2-methyl-phenol, and 3-amino-2-methyl-phenol;and

[0048] heterocyclic derivatives such as:3,4-dihydro-2H-1,4-benzoxazin-6-ol,4-methyl-2-phenyl-2,4-dihydro-3H-pyrazol-3-one, 1,3-benzodioxol-5-ol,1,3-benzodioxol-5-amine, 1H-indol-4-ol, 1H-indole-5,6-diol,1H-indol-7-ol, 1H-indol-5-ol, 1H-indol-6-ol, 1H-indole-2,3-dione,pyridine-2,6-diamine, and 2-aminopyridin-3-ol.

[0049] Most preferred primary intermediates include:

[0050] p-phenylenediamine derivatives such as:2-methyl-benzene-1,4-diamine, benzene-1,4-diamine,2-(2,5-diamino-phenyl)-ethanol, 1-(2,5-diamino-phenyl)-ethanol, and2-[(4-amino-phenyl)-(2-hydroxy-ethyl)-amino]-ethanol;

[0051] p-aminophenol derivatives such as: 4-amino-phenol,4-methylamino-phenol, 4-amino-3-methyl-phenol, and1-(5-amino-2-hydroxy-phenyl)-ethane-1,2-diol;

[0052] o-aminophenols such as: 2-amino-phenol, 2-amino-5-methyl-phenol,2-amino-6-methyl-phenol, and N-(4-amino-3-hydroxy-phenyl)-acetamide; and

[0053] heterocyclic derivatives such as: pyrimidine-2,4,5,6-tetramine,2-(4,5-diamino-1H-pyrazol-1-yl )ethanol,1-(4-methylbenzyl)-1H-pyrazole-4,5-diamine, and1-(benzyl)-1H-pyrazole-4,5-diamine.

[0054] Most preferred couplers include:

[0055] phenols, resorcinol and naphthol derivatives such as:benzene-1,3-diol, 4-chlorobenzene-1,3-diol, naphthalen-1-o,2-methyl-naphthalen-1-ol, and 2-methyl-benzene-1,3-diol;

[0056] m-phenylenediamine such as: 2-(2,4-diamino-phenoxy)-ethanol,2-(3-amino-4-methoxy-phenylamino)-ethanol,2-[2,4-diamino-5-(2-hydroxy-ethoxy)-phenoxy]-ethanol, and3-(2,4-diamino-phenoxy)-propan-1-ol;

[0057] m-aminophenols such as: 3-amino-phenol, 5-amino-2-methyl-phenol,5-(2-hydroxy-ethylamino)-2-methyl-phenol, and 3-amino-2-methyl-phenol;and

[0058] heterocyclic derivatives such as:3,4-dihydro-2H-1,4-benzoxazin-6-ol,4-methyl-2-phenyl-2,4-dihydro-3H-pyrazol-3-one, 1H-indol-6-ol, and2-aminopyridin-3-ol.

[0059] Understandably, the coupler compounds and the primaryintermediate compounds, including the novel compounds of the invention,in so far as they are bases, can be used as free bases or in the form oftheir physiologically compatible salts with organic or inorganic acids,such as hydrochloric, citric, acetic, tartaric, or sulfuric acids, or,in so far as they have aromatic OH groups, in the form of their saltswith bases, such as alkali phenolates.

[0060] The total amount of dye precursors (e.g., primary intermediateand coupler compounds, including the novel compounds of this invention)in the hair dyeing compositions of this invention is generally fromabout 0.002 to about 20, preferably from about 0.04 to about 10, andmost preferably from about 0.1 to about 7.0 weight percent, based on thetotal weight of the hair dyeing composition. The primary intermediateand coupler compounds are generally used in molar equivalent amounts.However, it is possible to use the primary intermediate compounds ineither excess or deficiency, i.e., a molar ratio of primary intermediateto coupler generally ranging from about 5:1 to about 1:5.

[0061] The hair dyeing compositions of this invention will contain theprimary intermediate of this invention in an effective dyeing amount,generally in an amount of from about 0.001 to about 10 weight percent byweight of the hair dye composition, preferably from about 0.01 to about5.0 weight percent. Other primary intermediates, when present, aretypically present in an amount such that in aggregate the concentrationof primary intermediates in the composition is from about 0.002 to about10 weight percent, preferably from about 0.01 to about 5.0 weightpercent. The coupler(s) are present in an effective dyeingconcentration, generally an amount of from about 0.001 to about 10.0weight percent by weight of the hair dye composition, preferably fromabout 0.01 to about 5.0 weight percent. The remainder of the hair dyecomposition comprises a carrier or vehicle for the couplers and primaryintermediates, and comprises various adjuvants as described below.

[0062] Any suitable carrier or vehicle, generally an aqueous orhydroalcoholic solution, can be employed, preferably an aqueoussolution. The carrier or vehicle will generally comprise more than 80weight percent of the hair dye composition, typically 90 to 99 weightpercent, preferably 94 to 99 weight percent. The hair coloringcompositions of this invention may contain as adjuvants one or morecationic, anionic, amphoteric, or zwitterionic surface active agents,perfumes, antioxidants such as ascorbic acid, thioglycolic acid orsodium sulfite, chelating and sequestering agents such as EDTA,thickening agents, alkalizing or acidifying agents, solvents, diluents,inerts, dispersing agents, penetrating agents, defoamers, enzymes, andother dye agents (e.g., synthetic direct and natural dyes). Theseadjuvants are cosmetic additive ingredients commonly used incompositions for coloring hair.

[0063] The hair dye compositions of the present invention are used byadmixing them with a suitable oxidant, which reacts with the hair dyeprecursors to develop the hair dye. Any suitable oxidizing agent can beemployed in the hair dye product compositions of this invention,particularly hydrogen peroxide (H₂O₂) or precursors therefor. Alsosuitable are urea peroxide, the alkali metal salts of persulfate,perborate, and percarbonate, especially the sodium salt, and melamineperoxide. The oxidant is usually provided in an aqueous compositiongenerally referred to as the developer composition, which normally isprovided as a separate component of the finished hair dye product andpresent in a separate container. The developer composition may alsocontain, to the extent compatible, various ingredients needed to formthe developer composition, i.e., peroxide stabilizers, foam formers,etc., and may incorporate one or more of the adjuvants referred toabove, e.g., surface active agents, thickeners, pH modifiers, etc. Uponmixing the hair coloring composition and the developer composition toform a hair dye product composition, the adjuvants are provided in thehair dye product composition as it is applied to the hair to achievedesired product attributes, e.g., pH, viscosity, rheology, etc.

[0064] The form of the hair dye product compositions according to theinvention can be, for example, a solution, especially an aqueous oraqueous-alcoholic solution. However, the form that is preferred is athick liquid, cream, gel or an emulsion whose composition is a mixtureof the dye ingredients with the conventional cosmetic additiveingredients suitable for the particular preparation.

[0065] Suitable conventional cosmetic additive ingredients useful in thehair dye and developer compositions, and hence in the hair dye productcompositions of this invention are described below, and may be used toobtain desired characteristics of the hair dye, developer and hair dyeproduct compositions.

[0066] Solvents: In addition to water, solvents that can be used arelower alkanols (e.g., ethanol, propanol, isopropanol, benzyl alcohol);polyols (e.g., carbitols, propylene glycol, hexylene glycol, glycerin).See WO 98/27941 (section on diluents) incorporated by reference. Seealso U.S. Pat. No. 6,027,538 incorporated by reference. Under suitableprocessing, higher alcohols, such as C8 to C18 fatty alcohols,especially cetyl alcohol, are suitable organic solvents, provided theyare first liquified by melting, typically at low temperature (50 to 80°C.), before incorporation of other, usually lipophilic, materials.

[0067] The organic solvents are typically present in the hair dyecompositions in an amount of from about 5 to about 30% by weight of thehair dye composition. Water is usually present in an amount of fromabout 5 to about 90% by weight of the hair dye composition, preferablyfrom about 15 to about 75% by weight and most preferably from about 30to about 65% by weight.

[0068] Surfactants: These materials are from the classes of anionic,cationic, amphoteric (including zwitterionic surfactants) or nonionicsurfactant compounds. (Cationic surfactants, generally included as hairconditioning materials, are considered separately below.) Suitablesurfactants, other than cationic surfactants, include fatty alcoholsulfates, ethoxylated fatty alcohol sulfates, alkylsulfonates,alkylbenzensulfonates, alkyltrimethylammonium salts, alkylbetaines,ethoxylated fatty alcohols, ethoxylated fatty acids, ethoxylatedalkylphenols, block polymers of ethylene and/or propylene glycol,glycerol esters, phosphate esters, fatty acid alkanol amides andethoxylated fatty acid esters, alkyl sulfates, ethoxylated alkylsulfates, alkyl glyceryl ether sulfonates, methyl acyl taurates, acylisethionates, alkyl ethoxy carboxylates, fatty acid mono- anddiethanolamides. Especially useful are sodium and ammonium alklylsulfates, sodium and ammonium ether sulfates having 1 to 3 ethyleneoxide groups, and nonionic surfactants sold as Tergitols, e.g., C11-C15Pareth-9, and Neodols, e.g., C12-C₁₅ Pareth-3. They are included forvarious reasons, e.g., to assist in thickening, for forming emulsions,to help in wetting hair during application of the hair dye productcomposition, etc. Amphoteric surfactants include, for example, theasparagine derivatives as well betaines, sultaines, glycinates andpropionates having an alkyl or alkylamido group of from about 10 toabout 20 carbon atoms. Typical amphoteric surfactants suitable for usein this invention include lauryl betaine, lauroamphoglycinate,lauroamphopropionate, lauryl sultaine, myristamidopropyl betaine,myristyl betaine, stearoamphopropylsulfonate, cocamidoethyl betaine,cocamidopropyl betaine, cocoamphoglycinate, cocoamphocarboxypropionate,cocoamphocarboxyglycinate, cocobetaine, and cocoamphopropionate.Reference is made to WO 98/52523 published Nov. 26, 1998 and WO 01/62221published Aug. 30, 2001, both incorporated herein by reference thereto.

[0069] The amount of surfactants in the hair dye compositions isnormally from about 0.1 % to 30% by weight, preferably 1 % to 15% byweight.

[0070] Thickeners: Suitable thickeners include such as higher fattyalcohols, starches, cellulose derivatives, petrolatum, paraffin oil,fatty acids and anionic and nonionic polymeric thickeners based onpolyacrylic and polyurethane polymers. Examples are hydroxyethylcellulose, hydroxymethylcellulose and other cellulose derivatives,hydrophobically modified anionic polymers and nonionic polymers,particularly such polymers having both hydrophilic and hydrophobicmoieties (i.e., amphiphilic polymers). Useful nonionic polymers includepolyurethane derivatives such as PEG-150/stearyl alcohol/SDMI copolymer.Suitable polyether urethanes are Aculyn® 22, 44 and Aculyn® 46 polymerssold by Rohm & Haas. Other useful amphiphilic polymers are disclosed inU.S. Pat. No. 6,010,541 incorporated by reference. See also WO 01/62221mentioned above. Examples of anionic polymers that can be used asthickeners are acrylates copolymer, acrylates/ceteth-20 methacrylatescopolymer, acrylates/ceteth-20 itaconate copolymer, andacrylates/beheneth-25 acrylates copolymers. In the case of theassociative type of thickeners, e.g., Aculyns 22, 44 and 46, the polymermay be included in one of either the hair dye composition or thedeveloper composition of the hair dye product and the surfactantmaterial in the another. Thus, upon mixing of the hair dye and developercompositions, the requisite viscosity is obtained. The thickeners areprovided in an amount to provide a suitably thick product as it isapplied to the hair. Such products generally have a viscosity of from1000 to 100000 cps, and often have a thixotropic rheology.

[0071] pH Modifying agents: Suitable materials that are used to adjustpH of the hair dye compositions include alkalizers such alkali metal andammonium hydroxides and carbonates, especially sodium hydroxide andammonium carbonate, ammonia, organic amines includingmethylethanolamine, aminomethylpropanol, mono-, di-, andtriethanolamine, and acidulents such as inorganic and inorganic acids,for example phosphoric acid, acetic acid, ascorbic acid, citric acid ortartaric acid, hydrochloric acid, etc. See U.S. Pat. No. 6,027,538incorporated by reference.

[0072] Conditioners: Suitable materials include silicones and siliconederivatives; hydrocarbon oils; monomeric quaternary compounds, andquaternized polymers. Monomeric quaternary compounds are typicallycationic compounds, but may also include betaines and other amphotericand zwitterionic materials that provide a conditioning effect. Suitablemonomeric quaternary compounds include behentrialkonium chloride,behentrimonium chloride, benzalkonium bromide or chloride, benzyltriethyl ammonium chloride, bis-hydroxyethyl tallowmonium chloride,C12-18 dialkyldimonium chloride, cetalkonium chloride, ceteartrimoniumbromide and chloride, cetrimonium bromide, chloride and methosulfate,cetylpyridonium chloride, cocamidoproypl ethyldimonium ethosulfate,cocamidopropyl ethosulfate, coco-ethyldimonium ethosulfate,cocotrimonium chloride and ethosulfate, dibehenyl dimonium chloride,dicetyldimonium chloride, dicocodimonium chloride, dilauryl dimoniumchloride, disoydimonium chloride, ditallowdimonium chloride,hydrogenated tallow trimonium chloride, hydroxyethyl cetyl dimoniumchloride, myristalkonium chloride, olealkonium chloride, soyethomoniumethosulfate, soytrimonium chloride, stearalkonium chloride, and manyother compounds. See WO 98/27941 incorporated by reference. Quaternizedpolymers are typically cationic polymers, but may also includeamphoteric and zwitterionic polymers. Useful polymers are exemplified bypolyquaternium-4, polyquaternium-6, polyquaternium-7, polyquaternium-8,polyquaternium-9, polyquaternium-10, polyquaternium-22,polyquaternium-32, polyquaternium-39, polyquaternium-44 andpolyquaternium-47. Silicones suitable to condition hair are dimethicone,amodimethicone, dimethicone copolyol and dimethiconol. See also WO99/34770 published Jul. 15, 1999, incorporated by reference, forsuitable silicones. Suitable hydrocarbon oils would include mineral oil.

[0073] Conditioners are usually present in the hair dye composition inan amount of from about 0.01 to about 5% by weight of the composition.

[0074] Direct Dyes: The hair dyeing compositions according to theinvention can also contain compatible direct dyes including DisperseBlack 9, HC Yellow 2, HC Yellow 4, HC Yellow 15,4-nitro-o-phenylenediamine, 2-amino-6-chloro-4-nitrophenol, HC Red 3,Disperse Violet 1, HC Blue 2, Disperse Blue 3, and Disperse Blue 377.These direct dyes can be contained in the hair coloring compositions ofthe invention in an amount of from about 0.05 to 4.0 percent by weight.

[0075] Natural ingredients: For example, proteins and proteinderivatives, and plant materials such as aloe, chamomile and hennaextracts.

[0076] Other adjuvants include polysaccharides, alkylpolyglycosides,buffers, chelating and sequestrant agents, antioxidants, and peroxidestabilizing agents as mentioned in WO 01/62221, etc.

[0077] The adjuvants referred to above but not specifically identifiedthat are suitable are listed in the International Cosmetics IngredientDictionary and Handbook, (Eighth Edition) published by The Cosmetics,Toiletry, and Fragrance Association, incorporated by reference. Inparticular reference is made to Volume 2, Section 3 (Chemical Classes)and Section 4 (Functions) are useful in identifying a specific adjuvantto achieve a particular purpose or multipurpose.

[0078] The above-mentioned conventional cosmetic ingredients are used inamounts suitable for their functional purposes. For example, thesurfactants used as wetting agents, associative agents, and emulsifiersare generally present in concentrations of from about 0.1 to 30 percentby weight, the thickeners are useful in an amount of from about 0.1 to25 percent by weight, and the hair care functional materials aretypically used in concentrations of from about 0.01 to 5.0 percent byweight.

[0079] The hair dyeing product composition as it is applied to the hair,i.e., after mixing the hair dye composition according to the inventionand the developer, can be weakly acidic, neutral or alkaline accordingto their composition. The hair dye compositions can have pH values offrom about 6 to 11.5, preferably from about 6.8 to about 10, andespecially from about 8 to about 10. The pH of the developer compositionis typically acidic, and generally the pH is from about 2.5 to about6.5, usually about 3 to 5. The pH of the hair dye and developercompositions is adjusted using a pH modifier as mentioned above.

[0080] In order to use the hair coloring composition for dyeing hair,the above-described hair coloring compositions according to theinvention are mixed with an oxidizing agent immediately prior to use anda sufficient amount of the mixture is applied to the hair, according tothe hair abundance, generally from about 60 to 200 grams. Some of theadjuvants listed above (e.g., thickeners, conditioners, etc.) can beprovided in the dye composition or the developer, or both, depending onthe nature of the ingredients, possible interactions, etc., as is wellknown in the art.

[0081] Typically, hydrogen peroxide, or its addition compounds withurea, melamine, sodium borate or sodium carbonate, can be used in theform of a 3 to 12 percent, preferably 6 percent, aqueous solution as theoxidizing agent for developing the hair dye. Oxygen can also be used asthe oxidizing agent. If a 6 percent hydrogen peroxide solution is usedas oxidizing agent, the weight ratio of hair coloring composition anddeveloper composition is 5:1 to 1:5, but preferably 1:1. In general, thehair dyeing composition comprising primary intermediate(s) andcoupler(s), including at least one of the compounds of formula (1), isprepared and then, at the time of use, the oxidizing agent, such asH₂0₂, contained in a developer composition is admixed therewith until anessentially homogenous composition is obtained, which is applied shortlyafter preparation to the hair to be dyed and permitted to remain incontact with the hair for a dyeing effective amount of time. The mixtureof the oxidizing agent and the dye composition of the invention (i.e.,the hair dye product composition) is allowed to act on the hair forabout 2 to about 60 minutes, preferably about 15 to 45, especially about30 minutes, at about 15 to 50° C., the hair is hair rinsed with water,and dried. If necessary, it is washed with a shampoo and rinsed, e.g.,with water or a weakly acidic solution, such as a citric acid ortartaric acid solution. Subsequently the hair is dried. Optionally, aseparate conditioning product may also be provided.

[0082] Together the hair dye composition of the present inventioncomprising the hair dye primary intermediate (1) and the developercomposition comprising the oxidizing agent form a system for dyeinghair. This system may be provided as a kit comprising in a singlepackage separate containers of the hair dye composition, the developer,the optional conditioner or other hair treatment product, andinstructions for use.

[0083] Especially useful primary intermediates of formula (1) of thisinvention will provide hair coloring compositions having outstandingcolor fastness, especially light fastness, fastness to washing andfastness to rubbing.

Dyeing Example 1

[0084] The following composition shown in Table 1 can be used for dyeingPiedmont hair. 100 g of the dyeing composition is mixed with 100 g 20volume hydrogen peroxide. The resulting mixture is applied to the hairand permitted to remain in contact with the hair for 30 minutes. Thedyed hair is then shampooed, rinsed with water and dried. The ranges ofingredients set out in Table 1 are illustrative of useful concentrationsof the recited materials in a hair dye product. TABLE 1 Composition forDyeing Hair Ingredients Range (wt %) Weight (%) Cocamidopropyl betaine 0-25 17.00 Polyquaternium-22 0-7 5.00 Monoethanolamine¹  0-15 2.00Oleic Acid  2-22 0.75 Citric Acid 0-3 0.10 28% Ammonium hydroxide¹  0-155.00 Behentrimonium chloride 1-5 0.50 Sodium sulfite 0-1 0.10 EDTA 0-10.10 Erythorbic acid 0-1 0.40 Ethoxydiglycol  1-10 3.50 C11-15 Pareth-9(Tergitol 15-S-9) 0.5-5   1.00 C12-15 Pareth-3 (Neodol 25-3) 0.25-5  0.50 Isopropanol  2-10 4.00 Propylene glycol  1-12 2.00p-phenylenediamine 0-5 1 mmole N,N-Bis(hydroxyethyl)-p-phenylene 0-5 1mmole diamine 3-Methyl-p-aminophenol 0-5 1 mmole p-Aminophenol 0-5 1mmole Primary Intermediate of this invention 0.5-5    4 mmoles5-Amino-2-Methyl Phenol² 0-5  3 mmoles 2,4-Diaminophenoxyethanol² 0-5  3mmoles M-Phenylenediamine² 0-5 1 mmole Water Qs to 100.00 qs to 100.00

[0085] Exemplary combinations of hair coloring components employing anovel primary intermediate of formula (1) of this invention are shown inTable 1 or in combinations C1 to C132 in Tables A through H. Readingdown the columns in Tables A through H, the Xes designate the dyecompounds (including the novel primary intermediates of the instantinvention) that form illustratively suitable combinations of dyes thatcan be formulated according to the present invention. For example, inCombination No. C1 in Column 4 of Table A, a primary intermediate ofFormula 1 of this invention, wherein y, R and Ar are definedhereinbefore, can be combined with 2-amino-phenol. Especially preferredas the primary intermediates in the combinations in Table 1 and C1 to C132 of Tables A through H are:

[0086] 2-(1-phenoxy-ethyl)-benzene-1,4-diamine;

[0087] 2-[1-(4-amino-3-methyl-phenoxy)-ethyl]-benzene-1,4-diamine;

[0088] 2-[1-(pyridin-3-yloxy)-ethyl]-benzene-1,4-diamine;

[0089] 2-[1-thien-2-yloxy)-ethyl]-benzene-1,4-diamine;

[0090] 2-[1-(furan-2-yloxy)-ethyl]-benzene-1,4-diamine;

[0091] 2-[1-(4-amino-phenoxy)-ethyl]-benzene-1,4-diamine;

[0092]2-{1-(2,3-dihydro-benzo[1,4]dioxin-6-yloxy)-ethyl}-benzene-1,4-diamine;

[0093] 2-[1-(5-bromo-fu ran-2yloxy)-ethyl]-benzene-1,4-diamine;

[0094] 2-[1-(4-chloromethyl-phenoxy)-ethyl]-benzene-1,4-diamine;

[0095] 2-[1-(4- methoxy-phenoxy)-ethyl]-benzene-1,4-diamine; and

[0096] 2-{1-(benzo[1,3]dioxin-5yloxy)-ethyl}-benzene-1,4-diamine. TABLEA Dye Combinations Structure IUPAC Name Name C1 C2 C3 C4 C5 C6 C7 C8 C9C10 C11

X X X X X X X X X X X

2-[(4-Amino-phenyl)-(2- hydroxy-ethyl)-amino]- ethanolN,N,-Bis(2-hydroxyethyl)- p-phenylene-diamine

4-Amino-phenol p-Aminophenol

4-Amimo-3-methyl- phenol 3-Methyl-p-aminophenol

2-Amino-phenol o-Aminophenol X X

Benzene-1,3-diol Resorcinol X X X

2-Nethyl-benzene-1,3-diol 2-Nethyl-resorcinol X X

Naphthalen-1-ol 1-Naphthol X

2-Methyl-naphthalen-1-ol 2-Methyl-1-naphthol X

2-(2,4-Diamino- phenoxy)-ethanol 2,4-Diamino-phenoxy- ethanol X

Benzene-1,3-diamine m-Phenylenediamine X

3-Amino-phenol m-Aminophenol X

5-Amino-2-methyl- phenol 2-Hydroxy-4- aminotoluene X

2-(4,5-Diamino-pyrazol- 1-yl)-ethanol 1-Hydroxyethyl-4,5-diamino-pyrazole

[0097] TABLE B Dye Combinations Structure C12 C13 C14 C15 C16 C17 C18C19 C20 C21 C22 C23 C24 C25 C26 C27 C28 C29

X X X X X X X X X X X X X X X X X X

X X X X

X X

X X X X X X X X

X X X X X X X X X

X X X

X X

X X

X X

X X

X X

[0098] TABLE C Dye Combinations Structure C30 C31 C32 C33 C34 C35 C36C37 C38 C39 C40 C41 C42 C43 C44 C45 C46 C47

X X X X X X X X X X X X X X X X X X

X X X X X X X X

x x

x X X X

x x

x X

X x

X x

X x x x

X x x x x x x x x x x

X x x x

c x x x x x x x x x x

[0099] TABLE D Dye Combinations Structure C48 C49 C50 C51 C52 C53 C54C55 C56 C57 C58 C59 C60 C61 C62 C63 C64 C65

X X X X X X X X X X X X X X X X X X

X X X X X

X X X X X X X X X

X X X X

X X

X X X X X X X

X X

X X

X X

X X

X X

X X

X X

[0100] TABLE E Dye Combinations Structure C66 C67 C68 C69 C70 C71 C72C73 C74 C75 C76 C77 C78 C79 C80 C81 C82 C83

X X X X X X X X X X X X X X X X X X

X X X X X

X X

X X X X X

X X

X X

X X X

X X

X X

x X

X

X X X X X X X X X X X X X

[0101] TABLE F Dye Combinations Structure C84 C85 C86 C87 C88 C89 C90C91 C92 C93 C94 C95 C96 C97 C98 C99 C100 C101

X X X X X X X X X X X X X X X X X X

X X X X X X X X X

X X X X X

X X

X X X X X X

X X

X X

X X

X X

X X

X X

X X

X X X X X X X X X X X X X X X X X X

[0102] TABLE G Dye Combinations Structure C102 C103 C104 C105 C106 C107C108 C109 C110 C111 C112 C113 C114 C115 C116 C117 C118 C119

X X X X X X X X X X X X X X X X X X

X X X X X X X X X X X X X X

X X X X X X X X X

X X X X X X X X X

X X

X X

X X

X X

X X

X X

X X

X X

X X X

X X X X

[0103] TABLE H Dye Combinations Structure C120 C121 C122 C123 C124 C125C126 C127 C128 C129 C130 C131 C132

X X X X X X X X X X X X X

X X X X X X X X X X X X X

X X X X

X

X

X

X

X

X X

X X

X X

X X

X X X X X X X X X

[0104] With the foregoing description of the invention, those skilled inthe art will appreciate that modifications may be made to the inventionwithout departing from the spirit thereof. Therefore, it is not intendedthat the scope of the invention be limited to the specific embodimentsillustrated and described.

We claim:
 1. A compound of formula (1):

wherein R is selected from the group consisting of hydrogen, hydroxy,nitro, amino, halogen, C₁ to C₅ alkyl or haloalkyl, C₁ to C₅ alkoxy orcyclic alkoxy, C₁ to C₅ hydroxyalkyl and C₁ to C₅ hydroxyalkoxy; Ar isan aromatic group; and y=1 to
 3. 2. A compound of claim 1 wherein R isselected from the group consisting of hydrogen, amino or C₁ to C₃ alkyl,and Ar is selected from the group consisting of phenyl, pyridinyl,furanyl, 2- or 3-thienyl, 2,3-dihydro-benzo[1,4]dioxin-5 or -6-yl orbenzo[1,3]dioxol-4 or -5-yl.
 3. A compound of claim 2 wherein Ar isphenyl.
 4. A compound of claim 2 wherein Ar is pyridinyl.
 5. A compoundof claim 2 wherein Ar is furanyl.
 6. A compound of claim 2 wherein Ar isthienyl.
 7. A process for the preparation of a compound of formula (1)of claim 1 comprising (a) reducing a compound of formula (2):

 with a reducing agent to produce a compound of formula (3)

(b) catalytically hydrogenating compound (3) to produce a compound offormula (4)

(c) subjecting the compound of formula (4) to tert-butoxycarbonylationto produce a compound of formula (5)

(d) subjecting the compound of formula (5) to the Mitsunobu reactionwith a compound of the formula HO—Ar—(R)_(y) to produce a compound offormula (6)

and (e) treating the compound of formula (6) with methanolic HCl toproduce a compound of formula (1)

wherein Ar, R and y are as defined in claim
 1. 8. A process according toclaim 7 wherein R is selected from the group consisting of hydrogen,amino or C₁ to C₃ alkyl, and Ar is selected from the group consisting ofphenyl, pyridinyl, furanyl, 2- or 3-thienyl,2,3-dihydro-benzo[1,4]dioxin-5 or -6-yl or benzo[1,3]dioxol-4 or -5-yl.9. A process according to claim 7 wherein Ar is phenyl.
 10. A processaccording to claim 7 wherein Ar is pyridinyl.
 11. A hair dye productcomprising a hair dyeing composition containing at least one primaryintermediate and at least one coupler and a developer compositioncontaining one or more oxidizing agents, the hair dyeing compositioncontaining a primary intermediate comprising a compound of formula (1):

wherein R is selected from the group consisting of hydrogen, hydroxy,nitro, amino, halogen, C₁ to C₅ alkyl or haloalkyl, C₁ to C₅ alkoxy orcyclic alkoxy, C₁ to C₅ hydroxyalkyl and C₁ to C₅ hydroxyalkoxy; Ar isan aromatic group; and y=1 to
 3. 12. A hair dye product according toclaim 11 wherein the hair dyeing composition additionally comprises aprimary intermediate selected from the group consisting of:2-methyl-benzene-1,4-diamine, benzene-1,4-diamine,2-(2,5-diamino-phenyl)-ethanol, 1-(2,5-diamino-phenyl)-ethanol,2-[(4-amino-phenyl)-(2-hydroxy-ethyl)-amino]-ethanol, 4-amino-phenol,4-methylamino-phenol, 4-amino-3-methyl-phenol,1-(5-amino-2-hydroxy-phenyl )-ethane-1,2-diol, 2-amino-phenol,2-amino-5-methyl-phenol, 2-amino-6-methyl-phenol,N-(4-amino-3-hydroxy-phenyl)-acetamide, pyrimidine-2,4,5,6-tetramine,2-(4,5-diamino-1H-pyrazol-1-yl)ethanol,1-(4-methylbenzyl)-1H-pyrazole-4,5-diamine, and1-(benzyl)-1H-pyrazole-4,5-diamine.
 13. A hair dye product according toclaim 11 wherein the coupler present in the hair dyeing composition isselected from the group consisting of: benzene-1,3-diol,4-chlorobenzene-1,3-diol, naphthalen-1-ol, 2-methyl-naphthalen-1-ol,2-methyl-benzene-1,3-diol, 2-(2,4-diamino-phenoxy)-ethanol,2-(3-amino-4-methoxy-phenylamino)-ethanol,2-[2,4-diamino-5-(2-hydroxy-ethoxy)-phenoxy]-ethanol, and3-(2,4-diamino-phenoxy)-propan-1-ol, 3-amino-phenol,5-amino-2-methyl-phenol, 5-(2-hydroxy-ethylamino)-2-methyl-phenol,3-amino-2-methyl-phenol, 3,4-dihydro-2H-1,4-benzoxazin-6-ol,4-methyl-2-phenyl-2,4-dihydro-3H-pyrazol-3-one, 1H-indol-6-ol, and2-aminopyridin-3-ol.
 14. A hair dye product according to claim 13wherein the hair dyeing composition additionally comprises a primaryintermediate selected from the group consisting of:2-methyl-benzene-1,4-diamine, benzene-1,4-diamine,2-(2,5-diamino-phenyl)-ethanol, 1-(2,5-diamino-phenyl)-ethanol,2-[(4-amino-phenyl)-(2-hydroxy-ethyl)-amino]-ethanol, 4-amino-phenol,4-methylamino-phenol, 4-amino-3-methyl-phenol,1-(5-amino-2-hydroxy-phenyl)-ethane-1,2-diol, 2-amino-phenol,2-amino-5-methyl-phenol, 2-amino-6-methyl-phenol,N-(4-amino-3-hydroxy-phenyl)-acetamide, pyrimidine-2,4,5,6-tetramine,2-(4,5-diamino-1H-pyrazol-1-yl)ethanol,1-(4-methylbenzyl)-1H-pyrazole-4,5-diamine, and1-(benzyl)-1H-pyrazole-4,5-diamine.
 15. A hair coloring system accordingto claim 11 wherein R is selected from the group consisting of hydrogen,amino or C₁ to C₃ alkyl, and Ar is selected from the group consisting ofphenyl, pyridinyl, furanyl, 2- or 3-thienyl,2,3-dihydro-benzo[1,4]dioxin-5 or -6-yl or benzo[1,3]dioxol-4 or -5-yl.16. In a hair dyeing system wherein at least one primary intermediate isreacted with at least one coupler in the presence of an oxidizing agentto produce an oxidative hair dye, the improvement wherein the at leastone primary intermediate comprises a compound of the formula (1):

wherein R is selected from the group consisting of hydrogen, hydroxy,nitro, amino, halogen, C₁ to C₅ alkyl or haloalkyl, C₁ to C₅ alkoxy orcyclic alkoxy, C₁ to C₅ hydroxyalkyl and C₁ to C₅ hydroxyalkoxy; Ar isan aromatic group; and y=1 to
 3. 17. A hair dyeing compositioncomprising, in a suitable carrier or vehicle, an effective hair dyeingamount of: (a) at least one coupler, and (b) at least one primaryintermediate comprising a compound of the formula (1):

wherein R is selected from the group consisting of hydrogen, hydroxy,nitro, amino, halogen, C₁ to C₅ alkyl or haloalkyl, C₁ to C₅ alkoxy orcyclic alkoxy, C₁ to C₅ hydroxyalkyl and C₁ to C₅ hydroxyalkoxy; Ar isan aromatic group; and y=1 to
 3. 18. A hair dyeing composition accordingto claim 17 additionally comprising a primary intermediate selected fromthe group consisting of: 2-methyl-benzene-1,4-diamine,benzene-1,4-diamine, 2-(2,5-diamino-phenyl)-ethanol,1-(2,5-diamino-phenyl)-ethanol,2-[(4-amino-phenyl)-(2-hydroxy-ethyl)-amino]-ethanol, 4-amino-phenol,4-methylamino-phenol, 4-amino-3-methyl-phenol,1-(5-amino-2-hydroxy-phenyl)-ethane-1,2-diol, 2-amino-phenol,2-amino-5-methyl-phenol, 2-amino-6-methyl-phenol,N-(4-amino-3-hydroxy-phenyl)-acetamide, pyrimidine-2,4,5,6-tetramine,2-(4,5-diamino-1H-pyrazol-1-yl)ethanol,1-(4-methylbenzyl)-1H-pyrazole-4,5-diamine, and1-(benzyl)-1H-pyrazole-4,5-diamine.
 19. A hair dyeing compositionaccording to claim 17 wherein the at least one coupler is selected fromthe group consisting of: benzene-1,3-diol, 4-chlorobenzene-1,3-diol,naphthalen-1-ol, 2-methyl-naphthalen-1-ol, 2-methyl-benzene-1,3-diol,2-(2,4-diamino-phenoxy)-ethanol,2-(3-amino-4-methoxy-phenylamino)-ethanol,2-[2,4-diamino-5-(2-hydroxy-ethoxy)-phenoxy]-ethanol, and3-(2,4-diamino-phenoxy)-propan-1-ol, 3-amino-phenol,5-amino-2-methyl-phenol, 5-(2-hydroxy-ethylamino)-2-methyl-phenol,3-amino-2-methyl-phenol, 3,4-dihydro-2H-1,4-benzoxazin-6-ol,4-methyl-2-phenyl-2,4-dihydro-3H-pyrazol-3-one, 1H-indol-6-ol, and2-aminopyridin-3-ol.
 20. A hair dyeing composition according to claim 19additionally comprising a primary intermediate selected from the groupconsisting of: 2-methyl-benzene-1,4-diamine, benzene-1,4-diamine,2-(2,5-diamino-phenyl)-ethanol, 1-(2,5-diamino-phenyl)-ethanol,2-[(4-amino-phenyl)-(2-hydroxy-ethyl)-amino]-ethanol, 4-amino-phenol,4-methylamino-phenol, 4-amino-3-methyl-phenol,1-(5-amino-2-hydroxy-phenyl)-ethane-1,2-diol, 2-amino-phenol,2-amino-5-methyl-phenol, 2-amino-6-methyl-phenol,N-(4-amino-3-hydroxy-phenyl)-acetamide, pyrimidine-2,4,5,6-tetramine,2-(4,5-diamino-1H-pyrazol-1-yl)ethanol,1-(4-methylbenzyl)-1H-pyrazole-4,5-diamine, and1-(benzyl)-1H-pyrazole-4,5-diamine.
 21. A hair dyeing compositionaccording to claim 17 wherein R is selected from the group consisting ofhydrogen, amino or C₁ to C₃ alkyl, and Ar is selected from the groupconsisting of phenyl, pyridinyl, furanyl, 2- or 3-thienyl,2,3-dihydro-benzo[1,4]dioxin-5 or -6-yl or benzo[1,3]dioxol-4 or -5-yl.22. A process for dyeing hair comprising forming a hair dye productcomposition by mixing a developer composition and a hair dyeingcomposition as defined in claim 17, applying to the hair an amount ofthe hair dye product composition effective to dye the hair, permittingthe hair dye product composition to contact the hair for period of timeeffective to dye the hair, and removing the hair dye product compositionfrom the hair.
 23. A process according to claim 22 wherein R is selectedfrom the group consisting of hydrogen, amino or C₁ to C₃ alkyl, and Aris selected from the group consisting of phenyl, pyridinyl, furanyl, 2-or 3-thienyl, 2,3-dihydro-benzo[1,4]dioxin-5 or -6-yl orbenzo[1,3]dioxol-4 or -5-yl.